Mixed detergent composition



Aug. 16, 1960 P. T. VITALE ET AL 2,949,425

MIXED DETERGENT COMPOSITION Filed May 28, 1956 Patented Aug'. 16, 1960Mixup DETERGENT COMPOSITION Peter T. Vitale, Fresh Meadows, and RobertLouis Bruns, Staten Island, N.Y., and Ralph Spencer Leonard, BerkeleyHeights, NJ., assignors to Colgate-Palmolive Company, New York, N.Y., acorporation of Delaware Filed May 28, 1956, Ser. No. 587 ,513

Claims. (Cl. 252-138) The present invention relates to a detergentcomposition characterized by controlled foaming power regulatedaccording to natural variations in water hardnesses and designed foroptimum relationship between foam and detergency which comprises a blendof water-soluble propylene tetramer benzene sulfonate and propylenepentamer benzene sulfonate detergents, and a water-soluble inorganicpolyphosphate forming water-soluble cornplexes with hard water salts, ashereinafter described and claimed.

In many household detergency operations, a high level of foaming powerhas considerable consumer appeal. Furthermore, many housewives consideror use a particular suds level or height as the sole or major criterionfor adequate concentration of the detergent composition in the Washingbath, regardless of the water hardness. For comparable detersiveeficiency, the use of hard water as the washing medium generallyrequires more detergent product than does the use of soft water. Thereis a natural variation moreover in the hardness depending upongeographical location and type of water treatment. Under suchconditions, the foaming power in Water of varying hardnesses is animportant consideration in the formulation of a successful andcommercially acceptable detergent composition. It would be advantageousto devise, if possible, a detergent `composition with a modied foambehavior that would be responsive and proportional to the water.hardness. Such a foam pattern would not falsely indicate the presence ofan adequate washing concentration. In contrast, the housewife would beconfronted with a vivid and realistic graphic representation of the needfor addition of more or less product to her wash depending mainly uponthe` water hardness.

Among the well known detergent materials are the various alkyl arylsulfonates. A particular commercial alkyl aryl sulfonate material is thepropylene tetramer benzene sulfonate detergent. This material possessesa fair amount of foaming power in soft water but does not exhibitoptimum performance unless relatively large quantities are added tO thewashing bath. The sudsing power of this tetrarner material iscomparatively high in hard Water. ene tetramer benzene sulfonate base asthe sole organic detergent may be considered as having a foam deficiencyin soft water and do not exhibit :the desired foam pattern outlinedabove.

It has now been Ifound that a detergent composition characterized bysuch controlled foaming power dependent in part upon water hardness andexhibiting other 'benecial properties can be formulated by a carefulchoice of ingredients and their proportions.

In accordance with the present invention, such detergent compositioncomprises a ternary combination of Water-soluble propylene tetramerbenzene sulfonate detergent, water-soluble propylene pentamer benzenesul- Detergent `compositions having a propyl-V fonate detergent andwater-soluble inorganic polyphosphate salt forming water-solublecomplexes with hard water salts, the ratio of the pentamer sulfonatedetergent to tetramer sulfonate detergent being from about 90:10 to70:30 Iby Weight, and theamount of said polyphosphate `salt beingsucient to sequester said hard water salts. Other significant featuresand preferred embodiments will be apparent in the following description.

This novel detergent composition is characterized by many desirableproperties. The particular blend of ingredients results in anall-purpose synthetic detergent composition which exhibits superiorperformance in all water hardnesses. There is exhibited a synergism infoaming power, particularly in soft Water at low concentrations in thewashing machine. In addition, the markedly increased foamingcharacteristics are properly balanced for Washing -baths of varyingwater hardnesses, i.e., the suds are more profuse in soft Water than inhard Water for a given concentration so that less detergent will be usedwhere less is actually needed. There is obtained a high level of washingpower, particularly in dishwashing performance andthe laundering ofsoiled textiles and the like. The pentamer sulfonate material whenemployed individually is particularly deficient inV foaming in hardwater but, in combination with the tetiarner sulfonate and saidpolyphosphate, there is achieved improved solubility, emulsication andfoaming propylene is polymerized to form a polypropylene product whichis essentially the tetramer and has an averageA molecular weightequivalent to a dodecyl group and a characteristic .branched-chainedstructure due to the polymerization. The propylene pentamer is formed`similarly by controlled polymerization of propylene. Benzene isalkylated with each of these propylene products in the presence of aFriedel-Crafts type catalyst, usually aluminurn chloride, hydrogenfluoride or sulfuric acid, to `form the corresponding propylene tetramerbenzene and propylene pentamer benzene materials. The pro ducts aresulfonated in known manner with a sulfonating agent, such as 20% oleumat 90 F., and neutralized with alkali to form the correspondingwater-soluble higher alkyl benzene sulfonate detergent salts. lt' ispreferred to use the alkali metal salts such as the sodium, potassiumyand lithium salts although other highly soluble salts such as theammonium, and lower alkylolarnine, e.g. monoand triethanolamine, saltsmay be employed also. l'In addition, the product contains varying`amounts of Water-soluble inorganic sulfate `salts resulting from theneutralization of the excess sulfuric acid employed in the sulfonationreaction.

The propylene tetrarner lbenzene material in the form of thecorresponding sul-fonate has been employed in Icommercial detergentcompositions. In general, the propylene tetramer benzene fraction 'nasan average molecular Weight of about 242450, as determined lby titrationof the benzidine :salt of the sulfonate material. It has an approximatedistillation range as follows: Initial BP. 500 F. minimum, BP. at 10%recovery S25-550 F., B.P. at 50% recovery S45-560 F., BP. at 95%recovery 590-600 F., and an endpoint of 635 F. maximum. A materialhaving the following analysis: Average M.W.-245, initial Bl". 526 F.,BP. at 10% recovery 543 F., B.P. at 50% recovery 558 F., B.P. atrecovery 581 F., etc., is illustrative of a typical propylene tet-rainermaterial. Where references are made The propylene pentamer benzenematerial has been found to vary according to the manufacturer such thatit may affect the performance of the corresponding sulfonate product. Ithas been found that the molecular weight and distillationcharacteristics `of the propylene pentamer benzene material provide acriterion for the determination and selection of those materials whichresult in superior performance Aof the ultimate mixed detergentcomposition. In correlating the distillation ranges with the perfomanceof the corresponding prppylene pentamer sulfonate, the extent of theboiling point ranges is an important consideration.. In general, thepropylene pentamer benzene should have an average molecular weight ofabout 260-310, preferably 27.0-300, a distillation forerun of less thanabout 50 F., prefer.- ably less than 30 F., kand a distillation centerYcut or middle range of less than 75 F., preferably less 'than 50 F. Theforerun is .the diterence in temperature between the initial boilingpoint, usually at least about 550 F., andthe boiling point at of thematerial distilled. The middle range is the difference in temperaturebetween the boiling points at 1.0% and 90% distilled. The

alkylated benzene may have such characteristics as manu-V factured in acontrolled manner or it maybe fractionated in any suitable manner.Examples of suitable propylene pentamer benzene materials have thefollowing approximate distillation ranges in degrees F.:

The Water-soluble inorganic polyphosphate salts which form water-solublecomplexes in hard Water are the alkali metal (including ammonium)tripolyphosphates and hexametaphosphates. Examples are sodiumtripolyphosphate, potassium tripolyphosphate, sodium hexametaphosphate(Cal-gon) andthe like. These materials are essential to perform avariety of functions related to the foaming power and detergency of thepresent compositions. Since the propylene pentamer benzene sulfonatedetergent forms insoluble salts with hard water salts, the saidpolyphosphate should be used in sutiicient quantities to aord ampleprotection for the pentamerbenzene sulfonate detergents against thecalcium and magnesiurn ions present in hard water. For example, it hasbeen found that at least about 0.05% of sodium tripolyphosphate isrequired in Water of 100 p.p.m. hardness (calculated as calciumcarbonate) and in the presence of 0.1% sodium propylene pentamer benzenesulfonate detergent. In the presence of hard water of 300 ppm., about0.15% sodium tripolyphosphate is required to neutralize the hardness,e.g. calcium ions, and permit said sulfonate detergent to exert maximumfoaming and washing power. These particular phosphate salts kresult alsoin optimum detergency and do not form insoluble salts with calci-um orKmagnesium ions which tend to deposit upon the ltextiles during theWashing and rinsing operation, as contrasted With other phosphatematerials such as sodium pyrophosphate which forms relatively insolublesalts with water hardness.

The specified phosphates exert unique foaming eifects in combinationwith the pentamer benzene sulfonate detergent. The presence of saidphosphates exerts a marked activating eifect on the foam due to theirpeculiar salt effect upon the pentamer benzene sulfonate detergent. Forexample, the sodium tripolyphosphate and hexarnetaphosphate improve thefoam of the pentamer .sulfonate markedly in distilled water and to adegree much greater than other salts, such as sodium sulfate, trisodiumphosphate or sodium pyrophosphate Whereas the elfect of all of thesebuilder salts upon the propylene tetramer benzene sulfonate isapproximately the same.

As indicated, the ratio of the propylene pentamer to tetramer benzenesulfonate detergents is an important consideration. It has been foundthat, where the ratio is from about 70:30 to 90:10 by weight andpreferably about :20, there is obtained a synergistic increase in thefoaming power in soft Water in the presence of the polyphosphate, ascompared to the effects obtained when using these sulfonate detergentsindividually. The mixed detergent composition Within these proportionsexhibits more sudsing power in soft water than in hard Water undercomparable conditions, and possesses the desired foam behavior patterntherefore.

In such Vbuilt compositions designed for laundering of soiled textilesand cleansing of household utensils and the like, the composition willhave the blend of the sulfonate detergents in said proportions, with thebalance being primarily Water-soluble inorganic builder salts havingabout 10 to 60% of said polyphosphate salt by Weight of the totalsolids. In general, the total amount of the propylene tetramer andpentamer sulfonatedetergents will be usually from about 5 to 50% byweight, preferably l0 to 40%, and said polyphosphate salts will be about10 to 60%, preferably about 20 to 60% by Weight on a dry basis, thebalance of total solids being primarily water-soluble norganc neutralsalts such asV sodium sulfate and the like.

These ingredients may be mixed in any suitable manner. The detergentcomposition is prepared preferably in particulate form by heat-drying inknown manner an aqueous slurry of `the ingredients, such as byspray-drying or drum-drying .the mixture at a temperature above 212 F.In such laundering mixtures in particulate form, the detergentcomposition may include various other substances employed in the lartgenerally `in such detergent composition provided that the use `of anysuch materials does not substantially adversely aifect the desiredeffects of the indicated combination of ingredients. These optionalmaterials may be inorganic or organic in structure and may be added tothe composition in any suitable manner, such as by addition to thecrutcher mixture prior to heat-drying. Examples of suitable materialsare alkali metal silicates and carbonates, alkali metal phosphates,alkali metal carboxymethylcellulose, lauric monoethanol amide, lauricdiethanolamide, optical brightener or fluorescent dye, fatty alcohols,perfume, color and the like.

The accompanying figures and data are illustrative of the nature of thepresent invention but it is to be understood that the invention is notlimited thereto. These ligures represent the results obtained by testingspecied detergent compositions under practical use conditions. 'Ihevarious curves shown `therein. are believed to have indicated criticalcurvatures based upon the test data. Theoretically, the specific shapeof the curves will be influenced in degree by modifications ofcompositions and conditions.

Figure 1 sets forth a series of curves obtained by plotting as theordinate the foam height in inches which 1s generated or remains at theend of a ten minute washing period during the washing at F. of a six`pound load of soiled textile items in an electric washing machine usingcompositions A and B separately in soft Water and in hard Water, versusthe total concentration of the detergent composition which is added tothe washing baths as the abscissa. Composition A comprises essentially35% mixed sodium alkyl benzene sulfonate detergent (4:1 of propylenepentamer to tetramer), 40% sodium tripolyphosphate, 20% sodium sulfatewith the balance being minor amounts of sodium silicate, sodiumcarboxymethylcellulose, moisture, fluorescent dye, perfume and the like.Composition B is essentially the same kexcept that it contains 35%sodium propylene tetramer benzene sulfonate detergent as the soleorganic detergent. The propylene tetramer benzene material beforesulfonation had the indicated typical analysis and the propylenepentamer benzene material before sulfonation had characteristics similarto that of material C previously set forth.

Certain facts will be noted from the curves obtained by use ofcomposition A characterizing the present invention and composition Bcorresponding to a commercial detergent composition:

(l) Composition B exhibits more foam in hard water than in soft water atthe lower concentrations, e.g. 0.l-0.3%, and essentially equal foam athigher concentrations.

(2) Composition A comprising the mixed detergents exhibits a diversefoam behavior pattern whereby much greater foam is generated in softwater than in hard water, particularly at the lower concentrations. Thisfoam pattern permits use of the accepted practice of the` housewifewhich employs sudsing power as a general guide or indicator of thedetergent concentration to beemployed in the washing machine. Forpurposes of illustration, it will be noted that a greater detergentconcentration is required in hard water to achieve a particular sudslevel than in soft Water.

(3) In general composition A gave a higher level of foam thancomposition B under most conditions.

The foam data are representative of the marked foam improvement over awide range of concentrations in the Washing machine which is obtained byuse of the specified blend of detergents in accordance with the presenrinvention. Similar foam improvement in washing machine tests areobservable in the ilash or initial suds volume, after addition of thesoiled load to the washing -machine, and during the course or the entirewashing operation.

Figure 2 represents a series of curves obtained as a result ofdishwashing performance of representative detergent compositions inpractical dishpan tests wherein a small amount of the detergentcomposition is added to a dishpan of water and greased dishes are washedby hand. The number of greased plates which can be washed before thefoam end-point or collapse of the foam furnishes an additional basis ofcomparison. In Figure 2 the number of greased plates washed until thefoam end point is plotted similarly against the concentration of thedetergent composition in soft water in the dishpan. In these tests acomposition comprising 35% sodium sulfonate detergent, 40% sodiumtripolyphosphate, 3% sodium carbonate and the balance sodium sulfate wasemployed for all of the test compositions which differed from oneanother only in the character of the sulfonate detergent. Composition Ccontained said 4:1 mixture of the propylene pentamer to propylenetetramer benzene sulfonate detergents, composition D had the propylenepentamer benzene sulfonate detergent solely, and composition E containedthe propylene tetramer benzene sulfonate as the sole organic detergent.

ItY will be apparent from Figure 2 that:

(1) Composition C of the present invention shows a synergistic increasein the number of plates Washed until the foam end-point is observed uponincreasing concentrations from above 0.1% to 0.4% by weight.

(2) Such effects are not predictable from the performance curves ofcompositions D and E containing the propylene pentamer and tetramerbenzene sulfonate detergents respectively.

In such dishwashing operations, there are a number of other signicantadvantages which are obtained with use of the detergent mixture. Thereis obtained a high degree of clarity of the washing solution andsuperior emulsication of the grease for longer periods of time using themixed detergents in comparison to the use of the same detergentsindividually.

The following examples are additional illustrations of compositions ofthe present invention. The proportions indicated are the approximateamounts by weight on a dry basis in the tinal detergent composition.

Compositions Ingredients I II III IV Polypropylene benzene sulfonatedetergents. 35 30 25 25 Sodium tripolyphosphate 40 40 40 50 Sodiumsilicate 7 7 7 7 Sodium sulfate 10 15 20 10 The balance being smallamounts of sodium carboxymethylcellulose, optical brightener, etc. Thepolypropylene benzene sulfonate detergent content is a 4:1 blend of thesodium propylene pentamer and tetramer benzene sulfonates.

The above ingredients for each composition are mixed at about 140 F. ina soap crutcher to form an aqueous slurry of about 60% solids. Thisslurry is submitted to spray-drying with heated air at a temperature ofabout 350 F. with a resultant moisture loss of almost 40%. The resultingcompositions are recovered in the form of beads and possess a highdegree of detersive and foaming properties in both hard and soft water.The foam behavior of these compositions is responsive to the waterhardness as previously described.

Although the present invention has been described and illustrated with areference to specic examples, it is understood that modications andVariations `of composition and procedure are contemplated within thescope of the appended claims.

Having thus described the invention, what is claimed 1s:

l. A detergent composition characterized by controlled foaming powerregulated according to variations in water hardnesses and consistingessentially of a ternary combination of Water-soluble propylene tetramerbenzene sulfonate detergent, water-soluble propylene pentamer benzenesulfonate detergent and water-soluble inorganic polyphosphate saltforming water-soluble complexes with hard water salts, the propylenetetramer benzene material of said sulfonate having an average molecularweight of about 242-250, the propylene pentamer lbenzene material ofsaid sulfonate having an average molecular weight of about 260-310 anddistillation ranges of less than about 50 F. from the initial boilingpoint to 10% recovery and less than 75 F. between the :boiling points at10% and 90% recovery, the ratio of the pentamer sul'fonate detergent totetramer sulfonate detergent being from 90:10 to 70:30 by weight, andthe amount of said polyphosphate salt being from about 10 to `60% byweight of the composition.

2. A detergent composition characterized by controlled foaming powerregulated according to variations in water hardnesses and consistingessentially of a ternary combination of water-soluble `propylenetetramer benzene sulfonate detergent, Water-soluble propylene pentamerbenzene sulfonate detergent and water-soluble inorganic tripolyphosphatesalt, the propylene tetramer benzene material of said sulfonate havingan average molecular weight of about 242-250, the propylene pentamerbenzene material of said sulfonate having an average molecular weight ofabout 260-310 and ydistillation ranges oft less than about 50 F. fromthe initial boiling point to 10% recovery and less than 75 F. betweenboiling points at 10% and 90% recovery, the ratio of the pentamersulfonate detergent to tetramer sulfonate detergent being from :10 to70:30 by weight, and the amount of said tripolyphosphate salt being fromabout 10 to 60% by Weight of the composition.

3. A detergent composition characterized by controlled foaming powerregulated according .to variations in water hardnesses and consistingessentially of a ternary combination of sodium .propylene tetramerbenzene sulfonate detergent, sodium propylene pentamer benzene sulfonatevdetergent and sodium tripolyphosphate, lthe propylene tetramer benzenematerial of said sulfonate having an average molecular weight of about242-250, the propylene pentamer benzene ymaterial of said sulfonatehaving an average molecular Weight of about 260-310 and distillationranges of less than about 50 F. from the initial boiling point to 10%recovery and less than 75 F. between the boiling points at 10% and 90%recovery, the ratio of the pentamer sulfonate detergent -to tetramersulfonate detergent being from 90: 10 to 70:30 by weight, and the amountof said sodium tripolyphosphate salt being from about 10 to 60% byweight of the composition.

4. A detergen-t composition characterized by controlled foaming powerregllated according to variations in Water hardnesses and consistingessentially of about to 50% by weight of a mixture of sodium propylenetetratner benzene sulfonate detergent and .sodium propylene pentamersulfonate detergent, the propylene tetramer benzene material of saidsulfo'nate having an average molecular weight of about 242250, .thepropylene pentamer benzene material of said sulfonate having an averagemolecular weight of about 260-310 and distillation ranges of less thanabout 50 F. from the initial boiling point to recovery and less than 75F. between the boiling .points at 10% and 90% recovery, the ratio of thepentamer sulfonate detergent to tetrarner sulfonate detergent being from90:10 to 70:30 by weight, and the balance of the composition beingprimarily water-soluble inorganic builder salts having about 10 to 60%of sodium tripolyphosphate by weight of the total solids.

5. A detergent composition characterized by controlled foaming powerregulated according to variations in Water hardnesses and consistingessentially lof a ternary combination of sodium propylene tetramerbenzene sulfonate detergent, sodium propylene pentamer benzene sulfonatedetergent and sodium tripolyphosphate, the propylene tetramer benzenematerial of said sulfonate having an average molecular weight of about242-250 and a distillation range having an initial boiling point of 500F, minimum, a boiling point at 10% recovery of 525-550 F., a boilingpoint at recovery of S45-560 IF., a boiling point at 95% recovery of590-600 F. and an end point of 635 F. maximum, the propylene pentamerbenzene material of said sulfonate having an average molecular weight ofabout 260-310 and a distillation range having an initial boiling pointof 550 F., less than about 50 F. from the initial boil-ing .point to 10%recovery and less than F. between the boiling points at 10% and 90%recovery, the ratio of the said pentamer sulfona-te detergent ltotetramer sulfonate detergent being from about :10 to 70:30 by weight,and the amount of said sodium tripolyphosphate salt being yfrom about 10to 60% by Weight of the composition.

References Cited in the flle of this patent UNITED STATES PATENTS

1. A DETERGENT COMPOSITION CHARACTERIZED BY CONTROLLED FOAMING POWERREGULATED ACCORDING TO VARIATIONS IN WATER HARDNESSES AND CONSISTINGESSENTIALLY OF A TERNARY COMBINATION OF WATER-SOLUBLE PROPYLENE TETRAMERBENZENE SULFONATE DETERGENT, WATER-SOLUBLE PROPYLENE PENTAMER BENZENESULFONATE DETERGENT AND WATER-SOLUBLE COMORGANIC POLYPHOSPHATE SALTFORMING WATER-SOLUBLE COMPLEXES WITH HARD WATER SALTS, THE PROPYLENETETRAMER BENZENE MATERIAL OF SAID SULFONATE HAVING AN AVERAGE MOLECULARWEIGHT OF ABOUT 242-250, THE PROPYLENE PENTAMER BENZENE MATERIAL OF SAIDSULFONATE HAVING AN AVERAGE MOLECULAR WEIGHT OF ABOUT 260-310 ANDDISTILLATION RANGES OF LESS THAN ABOUT 50*F. FROM THE INITIAL BOILINGPOINT TO 10% RECOVERY AND LESS THAN 75* F. BETWEEN THE BOILING POINTS AT10% AND 90% RECOVERY, THE RATIO OF THE PENTAMER SULFONATE DETERGENT TOTETRAMER SULFONATE DETERGENT BEING FROM 90: 10 TO 70:30 BY WEIGHT, ANDTHE AMOUNT OF SAID POLYPHOSPHATE SALT BEING FROM ABOUT 10 TO 60% BYWEIGHT OF THE COMPOSITION.